Process for the preparation of substituted TRIS(2-hydroxyphenyl)methane

ABSTRACT

Described is a novel process for the preparation of substituted tris(2-hydroxyphenyl)methane derivatives and the use of tris(2-hydroxyphenyl)methane derivatives for tertiary mineral oil production.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is application is the National Stage Entry of PCT/EP2014/053945,filed Feb. 28, 2014, which claims priority to European Application No.13158916.0, filed Mar. 13, 2013, the disclosures of which areincorporated herein by reference in their entireties.

TECHNICAL FIELD

The presently claimed invention is directed to a process for thepreparation of substituted tris(2-hydroxyphenyl)methane derivatives andthe use of tris(2-hydroxyphenyl)methane derivatives for tertiary mineraloil production.

BACKGROUND

In natural mineral oil deposits, mineral oil is often present in thecavities of porous reservoir rocks which are sealed toward the surfaceof the earth by impervious overlying strata. The cavities may be veryfine cavities, capillaries or pores. Fine pore necks may, for example,have a diameter of only approximately 1 μm. As well as mineral oil andproportions of natural gas, the deposits often also comprisesalt-containing water. More particularly, the use of assistants formineral oil production from salt-rich rock formations may be difficult.

In mineral oil production, a distinction is made between primary,secondary and tertiary production. In primary production, the mineraloil flows, after commencement of drilling of the deposit, of its ownaccord through the borehole to the surface due to the autogenouspressure of the deposit. The autogenous pressure results from the loadon the essentially water-filled overlying rock strata. However, theautogenous deposit pressure often declines rapidly in the course ofwithdrawal of mineral oil, and so it is usually possible to produce onlyapprox. 5 to 10% of the amount of mineral oil present in the deposit bymeans of primary production, according to the deposit. Thereafter, theautogenous pressure is no longer sufficient for production of mineraloil, and so pumps are often used thereafter for further mineral oilproduction.

After primary production, secondary production can therefore be used, inwhich, in addition to the boreholes which serve for production of themineral oil, called the production wells, further boreholes are drilledinto the mineral oil-bearing formation. These are called injection wellsand are used to inject water into the deposit (called “water flooding”),in order to maintain the pressure or increase it again.

As a result of the injection of water or of a corresponding aqueousformulation, the mineral oil is also forced gradually through thecavities in the formation, preceding from the injection well in thedirection of the production well. However, this only works for as longas the relatively high-viscosity oil is pushed onward by the water. Assoon as the mobile water breaks through to the production wells alongpreferred flow paths, it flows on the path of least resistance from thistime, i.e. particularly through the flow paths formed, and barelydisplaces any oil. By means of primary and secondary production,generally only approx. 30 to 35% of the amount of mineral oil present inthe deposit can be produced.

After the measures of secondary mineral oil production (or aftermeasures of primary mineral oil production), measures for tertiarymineral oil production (also known as “enhanced oil recovery”, EOR) arealso used to further enhance the oil yield. These include processes inwhich suitable chemicals, such as surfactants and/or polymers, are usedas assistants in formulations for oil production. An overview oftertiary oil production using chemicals can be found, for example, in anarticle by D. G. Kessel from 1989 (Journal of Petroleum Science andEngineering, 2 (1989), 81 to 101).

One of the known techniques for tertiary mineral oil production is thatknown as “polymer flooding”, in which an aqueous solution of athickening polymer is injected into the mineral oil deposit through theinjection wells, the viscosity of the aqueous polymer solution beingmatched to the viscosity of the mineral oil. Instead of a polymersolution, it is also possible to use aqueous solutions comprisingnonpolymeric thickeners.

Thickeners are chemicals which increase the viscosity of aqueoussolutions, extending as far as gel formation. The injection of athickened solution forces the mineral oil through the cavities in theformation preceding from the injection well in the direction of theproduction well, and allows the mineral oil to be produced through theproduction well. The fact that a thickener formulation has about thesame mobility as the mineral oil reduces the risk that the formulationbreaks through to the production well without having any effect(“fingering”).

Thus, it is possible with thickener to mobilize the mineral oil muchmore homogeneously and efficiently than in the case of use of mobilewater, by avoiding the occurrence of “fingering” in the case of use ofwater. Furthermore, piston-like displacement of the oil is achieved bythe matching of the mobility. This accelerates the production of themobile oil with regard to water flooding.

In addition, in the case of tertiary mineral oil production, it is alsopossible to use surfactants in addition to thickeners. Surfactants areused in mineral oil production in order to lower the oil-waterinterfacial tension to very low values and thus to mobilize furthermineral oil which would otherwise remain in the rock.

The subsequent injection of a thickened water solution forces themineral oil thus mobilized, as in the case of water flooding, precedingfrom the injection well in the direction of the production well, thusallowing it to be produced through the production well. Details offlooding with thickened or surfactant-containing solutions andcomponents suitable therefor are described, for example, in “Petroleum,Enhanced Oil Recovery” (Kirk-Othmer, Encyclopedia of ChemicalTechnology, John Wiley & Sons, 2005).

In some cases, such a combination of successive “surfactant flooding”and “polymer flooding” is preceded by a phase involving an alkalineagent such as sodium hydroxide solution, in order to mobilize naturalsurfactants present in the crude oil (“alkaline polymer-surfactantflooding”). For the aforementioned combination of successive “surfactantflooding” and “polymer flooding”, it is also possible to use what arecalled viscoelastic surfactants. These viscoelastic surfactants areinterface-active substances which, in solution, form associates whichincrease the viscosity of the solution.

For examples thereof, reference is made to “Molecular Gels: Materialswith Self-Assembled Fibrillar Networks” (Richard G. Weiss, PierreTerech, Dec. 22, 2005), Advances in Colliod and Interface Science128-130 (2006) 77-102). With viscoelastic surfactants, it is possible toachieve a reduction in interfacial tension which cannot be achieved withpolymeric components alone. Thickening surfactants for mineral oilproduction are described in various places. “Oilfield Reviews” (Vol.16(4) (2004) 10-28) describes the use of viscoelastic surfactant systemsas “fracturing fluids”. As early as 1985, V. Shvets described thestabilization of suspensions by the use of nonionic surfactants (Journalof Applied Chemistry of USSR, 58 (6), 1985, 1220-1224).

The so-called associates that surfactants can form are also calledmicelles and form due to hydrophobic interactions.

The thickening properties of such solutions can generally be eliminatedby shear, in which case the associates fall apart into smallerfragments. This operation, however, does not break any chemical bonds,and the associates develop their full thickening action again in theabsence of shear.

This is an advantage of viscoelastic surfactant systems, moreparticularly over synthetic polymeric thickeners, which can be destroyedirreversibly by strong shear, for example in the course of pumping of asolution into an oil reservoir. An additional effect is the fact thatviscoelastic surfactants lower the water-oil interfacial tension, whichis the case only to a distinctly lesser degree, if at all, for polymers.

However, in order to develop viscoelastic surfactant systems that caneconomically be used on a large scale for enhanced oil recovery, it isnecessary to develop a short route to tris(2-hydroxyphenyl)methanederivatives that is both economical and non-toxic.

G. Casiraghi et al. [Tetrahedron Letters, No. 9, 679-682 (1973)]describe the synthesis of tris(2-hydroxyphenyl)methane derivatives byreacting alkylphenoxy magnesium halides with triethylorthoformiate. Thereaction is effected by deprotonation of the phenol derivatives with aGrignard reagent and subsequent addition of triethylorthoformiate toafford tris-phenoxides. This reaction is also described in Dinger et al.[Eur. J. Org. Chem. 2000, 2467 2478].

The main disadvantages ensuing from synthesizingtris(2-hydroxyphenyl)methane derivatives by using Grignard reagents arethe general hazardousness of these reagents and the large amounts ofdifferent solvents that have to be used in order to keep the Grignardreagents in solution.

Another disadvantage of this protocol is the evolution of flammableethane gas upon generation of the magnesium salt by treatment of thephenol derivative with EtMgBr. Additionally, the use of stoichiometricamounts of magnesium with respect to the phenol is a disadvantage.

Hence, there is still a need to provide a process for the preparation oftris(2-hydroxyphenyl)methane derivatives via a short route with goodoverall yield under environmentally acceptable conditions, i.e. byavoiding large amounts of potentially toxic organic solvents.

SUMMARY

Embodiments of a first aspect of the present invention are directed to aprocess. A first embodiment is directed to a process for the preparationof a compound of general formula (I)

wherein R¹, R², R³ and R⁴, mutually independently, in each case denoteH; F; Cl; Br; I; —OH; —NO₂; —CN; —C(═O)—R⁶; —C(═O)—O—R⁷; —O—C(═O)—R⁸;—NH—C(═O)—R⁹; —C(═O)—NH₂; —C(═O)—NH—R¹⁰; —C(═O)—NR¹¹R¹²; —O—R¹³; —S—R¹⁴;—S(═O)—R¹⁵; —S(═O)₂—R¹⁶; unsubstituted or at least monosubstitutedalkyl; unsubstituted or at least monosubstituted heteroalkyl;unsubstituted or at least monosubstituted cycloalkyl; unsubstituted orat least monosubstituted cycloalkenyl; unsubstituted or at leastmonosubstituted heterocycloalkyl; unsubstituted or at leastmonosubstituted heterocycloalkenyl or unsubstituted or mono- orpolysubstituted aryl; and R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵and R¹⁶, mutually independently, in each case denote unsubstituted or atleast monosubstituted alkyl; unsubstituted or at least monosubstitutedalkenyl or unsubstituted or at least monosubstituted heteroalkyl; theprocess comprising at least the step of reacting at least one compoundof general formula (II)

wherein R¹, R², R³ and R⁴, mutually independently, in each case denoteH; F; Cl; Br; I; —OH; —NO₂; —CN; —C(═O)—R⁶; —C(═O)—O—R⁷; —O—C(═O)—R⁸;—NH—C(═O)—R⁹; —C(═O)—NH₂; —C(═O)—NH—R¹⁰; —C(═O)—NR¹¹R¹²; —O—R¹³; —S—R¹⁴;—S(═O)—R¹⁵; —S(═O)₂—R¹⁶; unsubstituted or at least monosubstitutedalkyl; unsubstituted or at least monosubstituted heteroalkyl;unsubstituted or at least monosubstituted cycloalkyl; unsubstituted orat least monosubstituted cycloalkenyl; unsubstituted or at leastmonosubstituted heterocycloalkyl; unsubstituted or at leastmonosubstituted heterocycloalkenyl; or unsubstituted or mono- orpolysubstituted aryl; and R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵and R¹⁶, mutually independently, in each case denote unsubstituted or atleast monosubstituted alkyl; unsubstituted or at least monosubstitutedalkenyl or unsubstituted or at least monosubstituted heteroalkyl; withat least one compound of general formula (III)

wherein R⁵, mutually independently, in each case denotes unsubstitutedor at least monosubstituted alkyl; in the presence of at least one Lewisacid.

In a second embodiment, the process of the first embodiment is modified,wherein the at least one Lewis acid is a metal-containing compoundselected from the group consisting of (a) AsX₃, GaX₃, BX₃, BX₃.(C₂H₅)₂O,BX₃.S(CH₃)₂, AlX₃, (C₂H₅)₂AlX, SbX₃, SbX₅, SnX₂, MgX₂, MgX₂.O(C₂H₅)₂,ZnX₂, BiX₃, FeX₂, TiX₂, TiX₄, NbX₅, NiX₂, CoX₂, HgX₂, wherein X in eachcase denotes F, Cl, Br or I, (b) BH₃, B(CH₃)₃, GaH₃, AlH₃,Al(acetate)(OH)₂, Al[OCH(CH₃)₂]₃, Al(OCH₃)₃, Al(OC₂H₅), Al₂O₃, (CH₃)₃Al,Ti[OCH(CH₃)₂]₃Cl, Ti[OCH(CH₃)₂]₄, methylaluminumdi-(2,6-di-tert-butyl-4-methylphenoxide), methylaluminumdi-(4-brom-2,6-di-tert-butylphenoxide), LiClO₄, (c) Mg(acetate)₂,Zn(acetate)₂, Ni(acetate)₂, Ni(NO₃)₂, Co(acetate)₂, Co(NO₃)₂,Cu(acetate)₂, Cu(NO₃)₂, Li(acetate), Zr(acetylacetonate)₄, Si(acetate)₄,K(acetate), Na(acetate), Cs(acetate), Rb(acetate), Mn(acetate)₂,Fe(acetate)₂, Bi(acetate)₃, Sb(acetate)₃, Sr(acetate)₂, Sn(acetate)₂,Zr(acetate)₂, Ba(acetate)₂, Hg(acetate)₂, Ag(acetate), Tl(acetate)₃, (d)Sc(fluoromethansulfonate)₃, Ln(fluoromethanesulfonate)₃,Ni(fluoromethanesulfonate)₂, Ni(tosylate)₂, Co(fluoromethanesulfonate)₂,Co(tosylate)₂, Cu(fluoromethanesulfonate)₂, and Cu(tosylate)₂.

In a third embodiment, the process of the first and second embodimentsis modified, wherein the at least one Lewis acid is a metal-containingcompound selected from the group consisting of AlX₃, SnX₂, MgX₂, ZnX₂,BiX₃, FeX₂, Al[OCH(CH₃)₂]₃, Al(OCH₃)₃ and Al(OC₂H₅)₃, wherein X in eachcase denotes F, Cl, Br, or I.

In a fourth embodiment, the process of the first through thirdembodiments is modified, wherein X denotes Cl.

In a fifth embodiment, the process of the first through fourthembodiments is modified, wherein the at least one Lewis acid is ametal-containing compound selected from the group consisting of AlCl₃,SnCl₂, MgCl₂, ZnCl₂, BiCl₃, FeCl₂, Al[OCH(CH₃)₂]₃, Al(OCH₃)₃, andAl(OC₂H₅)₃.

In a sixth embodiment, the process of the first embodiment is modified,wherein the molar ratio of the at least one compound of general formula(II) to the at least one compound of general formula (III) is in therange of 5.0:1.0 and 2.5:1.0.

In a seventh embodiment, the process of the first embodiment ismodified, wherein the concentration of the at least one metal-containingcompound in relation to the at least one compound of general formula(II) is in the range of 1 mol-% to 60 mol-%.

In an eighth embodiment, the process of the first through seventhembodiments is modified, wherein the at least one compound of generalformula (II) and the at least one compound of general formula (III) arereacted in at least one inert organic solvent selected from the groupconsisting of toluene, xylene, ortho-xylene, para-xylene, mesitylene,cyclohexane, cyclopentanone, benzonitrile, chlorobenzene,1,2-dichlorobenzene, 1,2-dichloroethane, dibutylether, anisol,butylacetate, methylethylketone, methylisobutylketone, pinacolone,dimethylformamide, and acetonitrile.

In a ninth embodiment, the process of the first through eighthembodiments is modified, wherein the at least one compound of generalformula (II) and the at least one compound of general formula (III) arereacted at a temperature in the range of 70° C. to 140° C. for a periodin the range of 2 to 20 hours.

In a tenth embodiment, the process of the first through ninthembodiments is modified, wherein the at least one compound of generalformula (II) and the at least one compound of general formula (III) arereacted in an inert solvent, wherein the molar concentration of the atleast one compound of general formula (II) is in the range of 1.0 M to8.0 M.

In an eleventh embodiment, the process of the first through tenthembodiments is modified, wherein R⁵ denotes unsubstituted C₁₋₅ alkyl.

In a twelfth embodiment, the process of the first through eleventhembodiments is modified, wherein R¹ and R³, mutually independently, ineach case denote H, F, Cl, Br, I, unsubstituted or at leastmonosubstituted C₁₋₁₂ alkyl, unsubstituted or at least monosubstitutedC₃₋₈ cycloalkyl, or unsubstituted or mono- or polysubstituted aryl; andR² and R⁴, in each case denote H.

In a thirteenth embodiment, the process of the first through twelfthembodiments is modified, wherein R¹ and R³, mutually independently, ineach case denote a moiety selected from the group consisting of methyl,ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl,1,1-dimethylpropyl, 2,2-dimethylpropyl, 3-methylbutyl, hexyl,2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,cyclopentyl, cyclohexyl, 1,1,3,3,-tetramethylbutyl, sec-butyl,CH₃—CH₂—C(CH₃)₂—, and unsubstituted phenyl; and R² and R⁴, in each casedenote H.

In a fourteenth embodiment, the process of the first through thirteenthembodiments is modified, wherein the compound of general formula (I) ispurified and isolated by applying the following steps: (a) adding aninert organic solvent and water to provide an organic phase and a waterphase; (b) separating the organic phase from the water phase; (c)optionally washing the organic phase with a 1N aqueous solution ofhydrochloric acid; (d) washing the organic phase with water; (e)filtering the organic phase to provide a residue and drying the residue.

DETAILED DESCRIPTION

Provided is a process for the preparation oftris(2-hydroxyphenyl)methane derivatives via a short route with goodoverall yield under environmentally acceptable conditions, i.e. byavoiding large amounts of potentially toxic organic solvents.

More specifically, provided is a process for the preparation of acompound of general formula (I)

wherein R¹, R², R³ and R⁴, mutually independently, in each case denoteH; F; Cl; Br; I; —OH; —NO₂; —CN; —C(═O)—R⁶; —C(═O)—O—R⁷; —O—C(═O)—R⁸;—NH—C(═O)—R⁹; —C(═O)—NH₂; —C(═O)—NH—R¹⁰; —C(═O)—NR¹¹R¹²; —O—R¹³; —S—R¹⁴;—S(═O)—R¹⁵; —S(═O)₂—R¹⁶; unsubstituted or at least monosubstitutedalkyl; unsubstituted or at least monosubstituted heteroalkyl;unsubstituted or at least monosubstituted cycloalkyl; unsubstituted orat least monosubstituted cycloalkenyl; unsubstituted or at leastmonosubstituted heterocycloalkyl; unsubstituted or at leastmonosubstituted heterocycloalkenyl; or unsubstituted or mono- orpolysubstituted aryl;andR⁶, R⁷, R⁸, R⁹; R¹⁰; R¹¹; R¹²; R¹³; R¹⁴; R¹⁵ and R¹⁶, mutuallyindependently, in each case denote unsubstituted or at leastmonosubstituted alkyl; unsubstituted or at least monosubstituted alkenylor unsubstituted or at least monosubstituted heteroalkyl;comprising at least the step of reacting at least one compound ofgeneral formula (II)

wherein R¹, R², R³ and R⁴, mutually independently, in each case denoteH; F; Cl; Br; I; —OH; —NO₂; —CN; —C(═O)—R⁶; —C(═O)—O—R⁷; —O—C(═O)—R⁸;—NH—C(═O)—R⁹; —C(═O)—NH₂; —C(═O)—NH—R¹⁰; —C(═O)—NR¹¹R¹²; —O—R¹³; —S—R¹⁴;—S(═O)—R¹⁵; —S(═O)₂—R¹⁶; unsubstituted or at least monosubstitutedalkyl; unsubstituted or at least monosubstituted heteroalkyl;unsubstituted or at least monosubstituted cycloalkyl; unsubstituted orat least monosubstituted cycloalkenyl; unsubstituted or at leastmonosubstituted heterocycloalkyl; unsubstituted or at leastmonosubstituted heterocycloalkenyl; or unsubstituted or mono- orpolysubstituted aryl;andR⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶, mutuallyindependently, in each case denote unsubstituted or at leastmonosubstituted alkyl; unsubstituted or at least monosubstituted alkenylor unsubstituted or at least monosubstituted heteroalkyl;with at least one compound of general formula (III)

wherein R⁵, mutually independently, in each case denotes unsubstitutedor at least monosubstituted alkyl;in the presence of at least one Lewis acid,whereinthe above-stated alkyl residues are in each case branched orstraight-chain and comprise 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12carbon atoms as chain links;the above-stated alkenyl residues are in each case branched orstraight-chain and comprise 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbonatoms as chain links;the above-stated heteroalkyl residues are in each case 3-, 4-, 5-, 6-,7-, 8-, 9-, 10-, 11- or 12-membered;the above-stated heteroalkyl residues comprise 1, 2, or 3 heteroatom(s)mutually independently selected from the group consisting of oxygen,sulfur and nitrogen as chain link(s);the above-stated alkyl residues, alkenyl residues and heteroalkylresidues may be substituted in each case with optionally 1, 2, 3, 4 or 5substituents mutually independently selected from the group consistingof F, Cl, Br, I, —NO₂, —CN, —OH, —SH, —NH₂, —N(C₁₋₅-alkyl)₂,—N(C₁₋₅-alkyl) (phenyl), —N(C₁₋₅-alkyl)(CH₂-phenyl),—N(C₁₋₅-alkyl)(CH₂—CH₂-phenyl), —C(═O)—H, —C(═O)—C₁₋₅-alkyl,—C(═O)-phenyl, —C(═S)—C₁₋₅-alkyl, —C(═S)-phenyl, —C(═O)—OH,—C(═O)—O—C₁₋₅-alkyl, —C(═O)—O-phenyl, —C(═O)—NH₂, —C(═O)—NH—C₁₋₅-alkyl,—C(═O)—N(C₁₋₅-alkyl)₂, —S(═O)—C₁₋₅-alkyl, —S(═O)-phenyl,—S(═O)₂—C₁₋₅-alkyl, —S(═O)₂-phenyl, —S(═O)₂—NH₂ and —SO₃H, wherein theabove-stated-C₁₋₅ alkyl residues may in each case be linear or branchedand the above-stated phenyl residues may, in one or more embodiments, besubstituted with 1, 2, 3, 4 or 5 substituents mutually independentlyselected from the group consisting of F, Cl, Br, I, —CN, —CF₃, —OH,—NH₂, —O—CF₃, —SH, —O—CH₃, —O—C₂H₅, —O—C₃H₇, methyl, ethyl, n-propyl,isopropyl, n-butyl, 2-butyl, isobutyl and tert.-butyl;the above-stated cycloalkyl residues in each case comprise 3, 4, 5, 6,7, 8, or 9 carbon atoms as ring members;the above-stated cycloalkenyl residues in each case comprise 3, 4, 5, 6,7, 8, or 9 carbon atoms as ring members;the above-stated heterocycloalkyl residues are in each case 3-, 4-, 5-,6-, 7-, 8-, or 9-membered;the above-stated heterocycloalkenyl residues are in each case 4-, 5-,6-, 7-, 8-, or 9-membered;the above-stated aryl residues in each case comprise 6, 10, or 14 carbonatoms;the above-stated heterocycloalkyl residues and heterocycloalkenylresidues in each case comprise 1, 2 or 3 heteroatom(s) mutuallyindependently selected from the group consisting of oxygen, sulfur andnitrogen (NH) as ring member(s);the above-stated aryl residues, cycloalkyl residues, cycloalkenylresidues, heterocycloalkyl residues and heterocycloalkenyl residues maybe substituted in each case with optionally 1, 2, 3, 4 or 5 substituentsmutually independently selected from the group consisting of F, Cl, Br,I, —CN, —NO₂, —OH, —SH, —NH₂, —C(═O)—OH, —C₁₋₅ alkyl,—(CH₂)—O—C₁₋₅-alkyl, —C₂₋₅ alkenyl, —C₂₋₅ alkynyl, —C≡C—Si(CH₃)₃,—C≡C—Si(C₂H₅)₃, —S—C₁₋₅-alkyl, —S-phenyl, —S—CH₂-phenyl, —O—C₁₋₅-alkyl,—O-phenyl, —O—CH₂-phenyl, —CF₃, —CHF₂, —CH₂F, —O—CF₃, —O—CHF₂, —O—CH₂F,—C(═O)—CF₃, —S—CF₃, —S—CHF₂, —S—CH₂F, —S(═O)₂-phenyl,—S(═O)₂—C₁₋₅-alkyl, —S(═O)—C₁₋₅-alkyl, —NH—C₁₋₅-alkyl, N(C₁₋₅alkyl)₂,—C(═O)—O—C₁₋₅-alkyl, —C(═O)—H; —C(═O)—C₁₋₅-alkyl, —CH₂—O—C(═O)-phenyl,—O—C(═O)-phenyl, —NH—S(═O)₂—C₁₋₅-alkyl, —NH—C(═O)—C₁₋₅-alkyl,—C(═O)—NH₂, —C(═O)—NH—C₁₋₅-alkyl, —C(═O)—N(C₁₋₅-alkyl)₂, pyrazolyl,phenyl, furyl (furanyl), thiazolyl, thiadiazolyl, thiophenyl (thienyl),benzyl and phenethyl, wherein the above-stated C₁₋₅ alkyl residues mayin each case be linear or branched and the cyclic substituents or thecyclic residues of these substituents themselves may be substituted withoptionally 1, 2, 3, 4, or 5, specifically with optionally 1, 2, 3, or 4,substituents mutually independently selected from the group consistingof F, Cl, Br, I, —CN, —NO₂, —OH, —SH, —NH₂, —C(═O)—OH, —C₁₋₅ alkyl,—(CH₂)—O—C₁₋₅-alkyl, —C₂₋₅ alkenyl, —C₂₋₅ alkynyl, —C≡C—Si(CH₃)₃,—C≡C—Si(C₂H₅)₃, —S—C₁₋₅-alkyl, —S-phenyl, —S—CH₂-phenyl, —O—C₁₋₅-alkyl,—O-phenyl, —O—CH₂-phenyl, —CF₃, —CHF₂, —CH₂F, —O—CF₃, —O—CHF₂, —O—CH₂F,—C(═O)—CF₃, —S—CF₃, —S—CHF₂ and —S—CH₂F.

For the purposes of the present invention, the term “alkyl” coversacyclic saturated hydrocarbon residues, which may be branched orstraight-chain and unsubstituted or at least monosubstituted with, as inthe case of C₁₋₁₂ alkyl, 1 to 12 (i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, or 12) C atoms. If one or more of the substituents denote an alkylresidue or comprise an alkyl residue which is mono- or polysubstituted,this may be substituted with optionally 1, 2, 3, 4, or 5, specificallywith 1, 2, or 3, substituents mutually independently selected from thegroup consisting of F, Cl, Br, I, —NO₂, —CN, —OH, —SH, —NH₂,—N(C₁₋₅-alkyl)₂, —N(C₁₋₅-alkyl)(phenyl), —N(C₁₋₅-alkyl) (CH₂-phenyl),—N(C₁₋₅-alkyl)(CH₂—CH₂-phenyl), —C(═O)—H, —C(═O)—C₁₋₅-alkyl,—C(═O)-phenyl, —C(═S)—C₁₋₅-alkyl, —C(═S)-phenyl, —C(═O)—OH,—C(═O)—O—C₁₋₅-alkyl, —C(═O)—O-phenyl, —C(═O)—NH₂, —C(═O)—NH—C₁₋₅-alkyl,—C(═O)—N(C₁₋₅-alkyl)₂, —S(═O)—C₁₋₅-alkyl, —S(═O)-phenyl,—S(═O)₂—C₁₋₅-alkyl, —S(═O)₂-phenyl, —S(═O)₂—NH₂ and —SO₃H, wherein theabove-stated-C₁₋₅ alkyl residues may in each case be linear or branchedand the above-stated phenyl residues may, in one or more embodiments, besubstituted with 1, 2, 3, 4 or 5 substituents mutually independentlyselected from the group consisting of F, Cl, Br, I, —CN, —CF₃, —OH,—NH₂, —O—CF₃, —SH, —O—CH₃, —O—C₂H₅, —O—C₃H₇, methyl, ethyl, n-propyl,isopropyl, n-butyl, 2-butyl, isobutyl and tert.-butyl. In one or moreembodiments, substituents may be selected mutually independently fromthe group consisting of F, Cl, Br, I, —NO₂, —CN, —OH, —SH, —NH₂,—N(CH₃)₂, —N(C₂H₅)₂ and N(CH₃)(C₂H₅).

The term “heteroalkyl” denotes an alkyl residue as described above, inwhich one or more C atoms have in each case been replaced by aheteroatom mutually independently selected from the group consisting ofoxygen, sulfur and nitrogen (NH). In one or more embodiments,heteroalkyl residues comprise 1, 2, or 3 heteroatom(s) mutuallyindependently selected from the group consisting of oxygen, sulfur andnitrogen (NH) as chain link(s). In one or more embodiments, heteroalkylresidues may be 3- to 12-membered.

Examples which may be mentioned of suitable heteroalkyl residues whichmay be unsubstituted or mono- or polysubstituted, are —CH₂—O—CH₃,—CH₂—O—C₂H₅, —CH₂—O—CH(CH₃)₂, —CH₂—O—C(CH₃)₃, —CH₂—S—CH₃, —CH₂—S—C₂H₅,—CH₂—S—CH(CH₃)₂, —CH₂—S—C(CH₃)₃, —CH₂—NH—CH₃, —CH₂—NH—C₂H₅,—CH₂—NH—CH(CH₃)₂, —CH₂—NH—C(CH₃)₃, —CH₂—CH₂—CO—CH₃, —CH₂—CH₂—O—C₂H₅,—CH₂—CH₂—O—CH(CH₃)₂, —CH₂—CH₂—O—C(CH₃)₃, —CH₂—CH₂—S—CH₃,—CH₂—CH₂—S—C₂H₅, —CH₂—CH₂—S—CH(CH₃)₂, —CH₂—CH₂—S—C(CH₃)₃,—CH₂—CH₂—NH—CH₃, —CH₂—CH₂—NH—C₂H₅, —CH₂—CH₂—NH—CH(CH₃)₂,—CH₂—CH₂—NH—C(CH₃)₃, —CH₂—S—CH₂—O—CH₃, —CH₂—O—CH₂—O—C₂H₅,—CH₂—O—CH₂—O—CH(CH₃)₂, —CH₂—S—CH₂—O—C(CH₃)₃, —CH₂—O—CH₂—S—CH₃,—CH₂—O—CH₂—S—C₂H₅, —CH₂—O—CH₂—S—CH(CH₃)₂, —CH₂—NH—CH₂—S—C(CH₃)₃,—CH₂—O—CH₂—NH—CH₃, —CH₂—O—CH₂—NH—C₂H₅, —CH₂—CO—CH₂—NH—CH(CH₃)₂,—CH₂—S—CH₂—NH—C(CH₃)₃ and —CH₂—CH₂—C(H)(CH₃)—(CH₂)₃—CH₃.

Examples of suitable substituted heteroalkyl residues which may bementioned are —(CH₂)—O—(CF₃), —(CH₂)—O—(CHF₂), —(CH₂)—O—(CH₂F),—(CH₂)—S—(CF₃), —(CH₂)—S—(CHF₂), —(CH₂)—S—(CH₂F), —(CH₂)—(CH₂)—O—(CF₃),—(CF₂)—O—(CF₃), —(CH₂)—(CH₂)—S—(CF₃) and —(CH₂)—(CH₂)—(CH₂)—O—(CF₃).

For the purpose of the present invention, the term “alkenyl” coversacyclic unsaturated hydrocarbon residues, which may be branched orstraight-chain and unsubstituted or at least mono-substituted andcomprise at least one double bond, specifically 1, 2, or 3 double bonds,with, as in the case of C₂-C₁₂ alkenyl, 2 to 30 (i.e. 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12) C atoms or with, as in the case of C₂-C₆ alkenyl, 2 to6 (i.e. 2, 3, 4, 5, or 6) C atoms. If one or more of the substituentsdenote an alkenyl residue or comprise an alkenyl residue which is mono-or polysubstituted, this may be substituted with optionally 1, 2, 3, 4,or 5, more specifically with 1, 2 or 3, substituents mutuallyindependently selected from the group consisting of F, Cl, Br, I, —NO₂,—CN, —OH, —SH, —NH₂, —N(C₁₋₅-alkyl)₂, —N(C₁₋₅-alkyl)(phenyl),—N(C₁₋₅-alkyl)(CH₂-phenyl), —N(C₁₋₅-alkyl)(CH₂—CH₂-phenyl), —C(═O)—H,—C(═O)—C₁₋₅-alkyl, —C(═O)-phenyl, —C(═S)—C₁₋₅-alkyl, —C(═S)-phenyl,—C(═O)—OH, —C(═O)—O—C₁₋₅-alkyl, —C(═O)—O-phenyl, —C(═O)—NH₂,—C(═O)—NH—C₁₋₅-alkyl, —C(═O)—N(C₁₋₅-alkyl)₂, —S(═O)—C₁₋₅-alkyl,—S(═O)-phenyl, —S(═O)₂—C₁₋₅-alkyl, —S(═O)₂-phenyl, —S(═O)₂—NH₂ and—SO₃H, wherein the above-stated-C₁₋₅ alkyl residues may in each case belinear or branched and the above-stated phenyl residues may besubstituted with 1, 2, 3, 4, or 5 substituents mutually independentlyselected from the group consisting of F, Cl, Br, I, —CN, —CF₃, —OH,—NH₂, —O—CF₃, —SH, —O—CH₃, —O—C₂H₅, —O—C₃H₇, methyl, ethyl, n-propyl,isopropyl, n-butyl, 2-butyl, isobutyl, and tert.-butyl. In one or moreembodiments, the substituents may be selected mutually independentlyfrom the group consisting of F, Cl, Br, I, —NO₂, —CN, —OH, —SH, —NH₂,—N(CH₃)₂, —N(C₂H₅)₂ and —N(CH₃)(C₂H₅).

For the purposes of the present invention, the term “cycloalkyl” means acyclic saturated hydrocarbon residue, with, in one or more embodiments,3, 4, 5, 6, 7, 8, or 9 C atoms, specifically with 3, 4, 5, 6, or 7 Catoms, very specifically with 5 or 6 C atoms, wherein the residue may beunsubstituted or monosubstituted or identically or differentlypolysubstituted. Examples which may be mentioned of suitable C₃₋₉cycloalkyl residues which may be unsubstituted or mono- orpolysubstituted are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl and cyclononyl. Examples of suitable C₃₋₇cycloalkyl residues which may be mentioned are cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl and cycloheptyl.

For the purposes of the present invention, the term “cycloalkenyl” meansa cyclic unsaturated hydrocarbon residue with, in one or moreembodiments, 3, 4, 5, 6, 7, 8, or 9 C atoms, specifically with 3, 4, 5,6, or 7 C atoms, very specifically with 5 or 6 C atoms, which comprisesat least one double bond, specifically one double bond, and may beunsubstituted or monosubstituted or identically or differentlypolysubstituted.

Examples which may be mentioned of suitable C₃₋₉ cycloalkenyl residueswhich may be unsubstituted or mono- or polysubstituted are cyclobutenyl,cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclononenyl andcyclooctenyl. Examples of suitable C₅₋₆ cycloalkenyl residues which maybe mentioned are cyclopentenyl and cyclohexenyl.

For the purposes of the present invention, the term “heterocycloalkyl”means a cyclic saturated hydrocarbon residue with, in one or moreembodiments, 3, 4, 5, 6, 7, 8, or 9 C atoms, specifically with 3, 4, 5,6, or 7 C atoms, very specifically with 5 or 6 C atoms, in which one ormore C atoms have in each case been replaced by a heteroatom mutuallyindependently selected from the group consisting of oxygen, sulfur andnitrogen (NH). In one or more embodiments, heterocycloalkyl residues maycomprise 1, 2, or 3 heteroatom(s) mutually independently selected fromthe group consisting of oxygen, sulfur and nitrogen (NH) as ringmember(s). A heterocycloalkyl residue may be unsubstituted ormonosubstituted or identically or differently polysubstituted. In one ormore embodiments, heterocycloalkyl residues may be 3- to 9-membered,specifically 3- to 7-membered, very specifically 5- to 7-membered.

Examples which may be mentioned of suitable 3- to 9-memberedheterocycloalkyl residues which may be unsubstituted or mono- orpolysubstituted are imidazolidinyl, tetrahydrofuranyl,tetrahydrothiophenyl, pyrrolidinyl, piperidinyl, morpholinyl,piperazinyl, thiomorpholinyl, tetrahydropyranyl, oxetanyl, azepanyl,azocanyl, diazepanyl, dithiolanyl, (1,3)-dioxolan-2-yl, isoxazolidinyl,isothioazolidinyl, pyrazolidinyl, oxazolidinyl, (1,2,4)-oxadiazolidinyl,(1,2,4)-thiadiazolidinyl, (1,2,4)-triazolidin-3-yl,(1,3,4)-thia-diazolidin-2-yl, (1,3,4)-triazolidin-1-yl,(1,3,4)-triazolidin-2-yl, tetrahydropyridazinyl, tetrahydropyrimidinyl,tetrahydropyrazinyl, (1,3,5)-tetrahydrotriazinyl,(1,2,4)-tetrahydrotriazin-1-yl, (1,3)-dithian-2-yl and(1,3)-thiazolidinyl. Examples of suitable 5- to 7-memberedheterocycloalkyl residues which may be mentioned are imidazolidinyl,tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, piperidinyl,morpholinyl, piperazinyl, thiomorpholinyl, tetrahydropyranyl, oxetanyl,azepanyl, diazepanyl and (1,3)-dioxolan-2-yl.

For the purposes of the present invention, the term “heterocycloalkenyl”means a cyclic unsaturated hydrocarbon residue with, in one or moreembodiments, 4, 5, 6, 7, 8, or 9 C atoms, specifically with 4, 5, 6, or7 C atoms, very specifically with 5 or 6 C atoms, which comprises atleast one double bond, specifically one double bond, and in which one ormore C atoms have in each case been replaced by a heteroatom mutuallyindependently selected from the group consisting of oxygen, sulfur andnitrogen (NH). In one or more embodiments, teterocycloalkenyl residuesmay comprise 1, 2, or 3 heteroatom(s) mutually independently selectedfrom the group consisting of oxygen, sulfur and nitrogen (NH) as ringmember(s). A heterocycloalkenyl residue may be unsubstituted ormonosubstituted or identically or differently polysubstituted. In one ormore embodiments, heterocycloalkenyl residues may be 4 to 9-membered,specifically 4- to 7-membered, very specifically 5- to 7-membered.

Examples which may be mentioned of suitable heterocycloalkenyl residuesor of suitable 5 to 7-membered heterocycloalkenyl residues which may beunsubstituted or mono- or polysubstituted are (2,3)-dihydrofuranyl,(2,5)-di-hydrofuranyl, (2,3)-dihydrothienyl, (2,5)-dihydrothienyl,(2,3)-dihydropyrrolyl, (2,5)-dihydropyrrolyl, (2,3)-dihydroisoxazolyl,(4,5)-dihydroisoxazolyl, (2,5)-dihydroisothiazolyl,(2,3)-dihydropyrazolyl, (4,5)-dihydropyrazolyl, (2,5)-dihydropyrazolyl,(2,3)-dihydrooxazolyl, (4,5)-dihydrooxazolyl, (2,5)-dihydrooxazolyl,(2,3)-dihydrothiazolyl, (4,5)-dihydrothiazolyl, (2,5)-dihydrothiazolyl,(2,3)-dihydroimidazolyl, (4,5)-dihydroimidazolyl,(2,5)-dihydroimidazolyl, (3,4,5,6)-tetrahydropyridin-2-yl,(1,2,5,6)-tetrahydropyridin-1-yl, (1, 2)-dihydropyridin-1-yl,(1,4)-dihydropyridin-1-yl, dihydropyranyl, and (1, 2, 3,4)-tetrahydropyridin-1-yl.

The cycloalkyl residues, heterocycloalkyl residues, cycloalkenylresidues or heterocycloalkenyl residues may for the purposes of thepresent invention be fused (anellated) with an unsubstituted or at leastmonosubstituted mono- or bicyclic ring system. For the purposes of thepresent invention, a mono- or bicyclic ring system should be understoodto mean monoor bicyclic hydrocarbon residues which may be saturated,unsaturated or aromatic and optionally comprise one or more heteroatomsas ring members. In one or more embodiments, the rings of theabove-stated mono- or bicyclic ring systems are in each case 4-, 5-, or6-membered and may in each case optionally comprise 0, 1, 2, 3, 4, or 5heteroatom(s), specifically optionally 0, 1, or 2 heteroatom(s) as ringmember(s), which are mutually independently selected from the groupconsisting of oxygen, nitrogen and sulfur. If a bicyclic ring system ispresent, the different rings may, in each case mutually independently,exhibit a different degree of saturation, i.e. be saturated, unsaturatedor aromatic.

Examples which may be mentioned of suitable cycloalkyl residues,heterocycloalkyl residues, cycloalkenyl residues or heterocyclalkenylresidues which may be unsubstituted or mono- or polysubstituted, and arefused with a mono- or bicyclic ring system, are(1,2,3,4)-tetrahydroquinolinyl, (1,2,3,4)-tetrahydroisoquinolinyl, (2,3)-dihydro-1H-isoindolyl, (1,2,3,4)-tetrahydronaphthyl,(2,3)-dihydrobenzo[1.4]dioxinyl, benzo[1.3]dioxolyl,(3,4)-dihydro-2H-benzo[1.4]oxazinyl andoctahydro-pyrrolo[3,4-c]pyrrolyl.

If one or more of the substituents denote any cycloalkyl residue,cycloalkenyl residue, heterocycloalkyl residue or heterocycloalkenylresidues which is at least monosubstituted, this may be substituted withoptionally 1, 2, 3, 4, or 5, specifically with optionally 1, 2, or 3,substituents mutually independently selected from the group consistingof F, Cl, Br, I, —CN, —NO₂, —OH, —SH, —NH₂, —C(═O)—OH, —C₁₋₅ alkyl,—(CH₂)—O—C₁₋₅-alkyl, —C₂₋₅ alkenyl, —C₂₋₅ alkynyl, —C≡C—Si(CH₃)₃,—C≡C—Si(C₂H₅)₃, —S—C₁₋₅-alkyl, —S-phenyl, —S—CH₂-phenyl, —O—C₁₋₅-alkyl,—O-phenyl, —O—CH₂-phenyl, —CF₃, —CHF₂, —CH₂F, —O—CF₃, —O—CHF₂, —O—CH₂F,—C(═O)—CF₃, —S—CF₃, —S—CHF₂, —S—CH₂F, —S(═O)₂-phenyl,—S(═O)₂—C₁₋₅-alkyl, —S(═O)—C₁₋₅-alkyl, —NH—C₁₋₅-alkyl, N(C₁₋₅alkyl)₂,—C(═O)—O—C₁₋₅-alkyl, —C(═O)—H; —C(═O)—C₁₋₅-alkyl, —CH₂—O—C(═O)-phenyl,—O—C(═O)-phenyl, —NH—S(═O)₂—C₁₋₅-alkyl, —NH—C(═O)—C₁₋₅-alkyl,—C(═O)—NH₂, —C(═O)—NH—C₁₋₅-alkyl, —C(═O)—N(C₁₋₅-alkyl)₂, pyrazolyl,phenyl, furyl (furanyl), thiazolyl, thiadiazolyl, thiophenyl (thienyl),benzyl and phenethyl, wherein the above-stated C₁₋₅ alkyl residues mayin each case be linear or branched and the cyclic substituents or thecyclic residues of these substituents themselves may be substituted withoptionally 1, 2, 3, 4, or 5, specifically with optionally 1, 2, 3, or 4,substituents mutually independently selected from the group consistingof F, Cl, Br, I, —CN, —NO₂, —OH, —SH, —NH₂, —C(═O)—OH, —C₁₋₅ alkyl,—(CH₂)—O—C₁₋₅-alkyl, —C₂₋₅ alkenyl, —C₂₋₅ alkynyl, —C≡C—Si(CH₃)₃,—C≡C—Si(C₂H₅)₃, —S—C₁₋₅-alkyl, —S-phenyl, —S—CH₂-phenyl, —O—C₁₋₅-alkyl,—O-phenyl, —O—CH₂-phenyl, —CF₃, —CHF₂, —CH₂F, —O—CF₃, —O—CHF₂, —O—CH₂F,—C(═O)—CF₃, —S—CF₃, —S—CHF₂ and —S—CH₂F.

In one or more embodiments, the substituents may be in each casemutually independently selected from the group consisting of F, Cl, Br,I, —CN, —NO₂, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,2-butyl, tert.-butyl, n-pentyl, neopentyl, ethenyl, allyl, ethynyl,propynyl, —C≡C—Si(CH₃)₃, —C≡C—Si(C₂H₅)₃, —CH₂—O—CH₃, —CH₂—O—C₂H₅, —OH,—SH, —NH₂, —C(═O)—OH, —S—CH₃, —S—C₂H₅, —S(═O)—CH₃, —S(═O)₂—CH₃,—S(═O)—C₂H₅, —S(═O)₂—C₂H₅, —O—CH₃, —O—C₂H₅, —O—C₃H₇, —O—C(CH₃)₃, —CF₃,—CHF₂, —CH₂F, —O—CF₃, —O—CHF₂, —O—CH₂F, —C(═O)—CF₃, —S—CF₃, —S—CHF₂,—S—CH₂F, —S(═O)₂-phenyl, pyrazolyl, phenyl, —N(CH₃)₂, —N(C₂H₅)₂,—NH—CH₃, —NH—C₂H₅, —CH₂—O—C(═O)-phenyl, —NH—S(═O)₂—CH₃, —C(═O)—O—CH₃,—C(═O)—O—C₂H₅, —C(═O)—O—C(CH₃)₃, —C(═O)—H, —C(═O)—CH₃, —C(═O)—C₂H₅,—NH—C(═O)—CH₃, —NH—C(═O)—C₂H₅, —O—C(═O)-phenyl, —C(═O)—NH₂,—C(═O)—NH—CH₃, —C(═O)—N(CH₃)₂, phenyl, furyl (furanyl), thiadiazolyl,thiophenyl (thienyl) and benzyl, wherein the cyclic substituents or thecyclic residues of these substituents themselves may in each case besubstituted with optionally 1, 2, 3, 4, or 5, specifically withoptionally 1, 2, 3, or 4, substituents mutually independently selectedfrom the group consisting of F, Cl, Br, I, —CN, —NO₂, —OH, —SH, —NH₂,—C(═O)—OH, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,2-butyl, tert.-butyl, n-pentyl, neopentyl, ethenyl, allyl, ethynyl,propynyl, —C≡C—Si(CH₃)₃, —C≡C—Si(C₂H₅)₃, —CH₂—O—CH₃, —CH₂—O—C₂H₅,—S—CH₃, —S—C₂H₅, —S(═O)—CH₃, —S(═O)₂—CH₃, —S(═O)—C₂H₅, —S(═O)₂—C₂H₅,—O—CH₃, —O—C₂H₅, —O—C₃H₇, —O—C(CH₃)₃, —CF₃, —CHF₂, —CH₂F, —O—CF₃,—O—CHF₂, —O—CH₂F, —C(═O)—CF₃, —S—CF₃, —S—CHF₂, and —S—CH₂F.

The term “aryl” means in the sense of this invention aromatichydrocarbons having up to 14 ring members, including phenyls andnaphthyls. Each aryl residue can be unsubstituted or mono- orpolysubstituted, wherein the aryl substituents can be the same ordifferent and in any desired and possible position of the aryl. The arylcan be bound to the superordinate general structure via any desired andpossible ring member of the aryl residue. The aryl residues can also becondensed with further saturated, (partially) unsaturated,(hetero)cyclic, aromatic or heteroaromatic ring systems, i.e. withcycloalkyl, heterocyclyl, aryl, or heteroaryl which can in turn beunsubstituted or mono- or polysubstituted. Examples of condensed arylresidues are benzodioxolanyl and benzodioxanyl. In one or moreembodiments, aryl is selected from the group containing phenyl,1-naphthyl and 2-naphthyl which can be respectively unsubstituted ormono- or polysubstituted. In one or more specific embodiments, aryl isphenyl, unsubstituted or mono- or polysubstituted.

In relation to “aryl”, the term “mono- or polysubstituted” refers in thesense of this invention to the single or multiple, for example double,triple or quadruple, substitution of one or more hydrogen atoms of thering system each independently of one another by substituents selectedfrom the group consisting of F, Cl, Br, I, —CN, —NO₂, —OH, —SH, —NH₂,—C(═O)—OH, —C₁₋₅ alkyl, —(CH₂)—O—C₁₋₅-alkyl, —C₂₋₅ alkenyl, —C₂₋₅alkynyl, —C≡C—Si(CH₃)₃, —C≡C—Si(C₂H₅)₃, —S—C₁₋₅-alkyl, —S-phenyl,—S—CH₂-phenyl, —O—C₁₋₅-alkyl, —O-phenyl, —O—CH₂-phenyl, —CF₃, —CHF₂,—CH₂F, —O—CF₃, —O—CHF₂, —O—CH₂F, —C(═O)—CF₃, —S—CF₃, —S—CHF₂, —S—CH₂F,—S(═O)₂-phenyl, —S(═O)₂—C₁₋₅-alkyl, —S(═O)—C₁₋₅-alkyl, —NH—C₁₋₅-alkyl,N(C₁₋₅alkyl)₂, —C(═O)—O—C₁₋₅-alkyl, —C(═O)—H; C(═O)—C₁₋₅-alkyl,—CH₂—O—C(═O)-phenyl, —O—C(═O)-phenyl, —NH—S(═O)₂—C₁₋₅-alkyl,—NH—C(═O)—C₁₋₅-alkyl, —C(═O)—NH₂, —C(═O)—NH—C₁₋₅-alkyl,—C(═O)—N(C₁₋₅-alkyl)₂, pyrazolyl, phenyl, furyl (furanyl), thiazolyl,thiadiazolyl, thiophenyl (thienyl), benzyl, and phenethyl, wherein theabove-stated C₁₋₅ alkyl residues may in each case be linear or branchedand the cyclic substituents or the cyclic residues of these substituentsthemselves may be substituted with optionally 1, 2, 3, 4, or 5,specifically with optionally 1, 2, 3, or 4, substituents mutuallyindependently selected from the group consisting of F, Cl, Br, I, —CN,—NO₂, —OH, —SH, —NH₂, —C(═O)—OH, —C₁₋₅ alkyl, —(CH₂)—O—C₁₋₅-alkyl, —C₂₋₅alkenyl, —C₂₋₅alkynyl, —C≡C—Si(CH₃)₃, —C≡C—Si(C₂H₅)₃, —S—C₁₋₅-alkyl,—S-phenyl, —S—CH₂-phenyl, —O—C₁₋₅-alkyl, —O-phenyl, —O—CH₂-phenyl, —CF₃,—CHF₂, —CH₂F, —O—CF₃, —O—CHF₂, —O—CH₂F, —C(═O)—CF₃, —S—CF₃, —S—CHF₂, and—S—CH₂F.

In one or more embodiments, the substituents may be in each casemutually independently selected from the group consisting of F, Cl, Br,I, —CN, —NO₂, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,2-butyl, tert.-butyl, n-pentyl, neopentyl, ethenyl, allyl, ethynyl,propynyl, —C≡C—Si(CH₃)₃, —C≡C—Si(C₂H₅)₃, —CH₂—O—CH₃, —CH₂—O—C₂H₅, —OH,—SH, —NH₂, —C(═O)—OH, —S—CH₃, —S—C₂H₅, —S(═O)—CH₃, —S(═O)₂—CH₃,—S(═O)—C₂H₅, —S(═O)₂—C₂H₅, —O—CH₃, —O—C₂H₅, —O—C₃H₇, —O—C(CH₃)₃, —CF₃,—CHF₂, —CH₂F, —O—CF₃, —O—CHF₂, —O—CH₂F, —C(═O)—CF₃, —S—CF₃, —S—CHF₂,—S—CH₂F, —S(═O)₂-phenyl, pyrazolyl, phenyl, —N(CH₃)₂, —N(C₂H₅)₂,—NH—CH₃, —NH—C₂H₅, —CH₂—O—C(═O)-phenyl, —NH—S(═O)₂—CH₃, —C(═O)—O—CH₃,—C(═O)—O—C₂H₅, —C(═O)—O—C(CH₃)₃, —C(═O)—H, —C(═O)—CH₃, —C(═O)—C₂H₅,—NH—C(═O)—CH₃, —NH—C(═O)—C₂H₅, —O—C(═O)-phenyl, —C(═O)—NH₂,—C(═O)—NH—CH₃, —C(═O)—N(CH₃)₂, phenyl, furyl (furanyl), thiadiazolyl,thiophenyl (thienyl), and benzyl, wherein the cyclic substituents or thecyclic residues of these substituents themselves may in each case besubstituted with optionally 1, 2, 3, 4, or 5, specifically withoptionally 1, 2, 3, or 4, substituents mutually independently selectedfrom the group consisting of F, Cl, Br, I, —CN, —NO₂, —OH, —SH, —NH₂,—C(═O)—OH, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,2-butyl, tert.-butyl, n-pentyl, neopentyl, ethenyl, allyl, ethynyl,propynyl, —C≡C—Si(CH₃)₃, —C≡C—Si(C₂H₅)₃, —CH₂—O—CH₃, —CH₂—O—C₂H₅,—S—CH₃, —S—C₂H₅, —S(═O)—CH₃, —S(═O)₂—CH₃, —S(═O)—C₂H₅, —S(═O)₂—C₂H₅,—O—CH₃, —O—C₂H₅, —O—C₃H₇, —O—C(CH₃)₃, —CF₃, —CHF₂, —CH₂F, —O—CF₃,—O—CHF₂, —O—CH₂F, —C(═O)—CF₃, —S—CF₃, —S—CHF₂, and —S—CH₂F.

In one or more embodiments, R⁵ denotes unsubstituted C₁₋₅ alkyl. Inspecific embodiments, R⁵ denotes a moiety selected from the groupconsisting of methyl, ethyl and iso-propyl.

In one or more embodiments, R¹ and R³, mutually independently, in eachcase denote H; F; Cl; Br; I; unsubstituted or at least monosubstitutedC₁₋₁₂ alkyl; unsubstituted or at least monosubstituted C₃₋₈ cycloalkyl;or unsubstituted or mono- or polysubstituted aryl; and R² and R⁴, ineach case denote H.

In one or more specific embodiments, R¹ and R³, mutually independently,in each case denote a moiety selected from the group consisting ofmethyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl,n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 3-methylbutyl, hexyl,2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,cyclopentyl, cyclohexyl, 1,1,3,3,-tetramethylbutyl, sec-butyl,CH₃—CH₂—C(CH₃)₂— and unsubstituted phenyl; and R² and R⁴, in each casedenote H.

In one or more embodiments, the at least one Lewis acid is ametal-containing compound selected from the group consisting of

-   a) AsX₃, GaX₃, BX₃, BX₃.(C₂H₅)₂O, BX₃.S(CH₃)₂, AlX₃, (C₂H₅)₂AlX,    SbX₃, SbX₅, SnX₂, MgX₂, MgX₂.O(C₂H₅)₂, ZnX₂, BiX₃, FeX₂, TiX₂, TiX₄,    NbX₅, NiX₂, CoX₂, HgX₂, whereby X in each case denotes F, Cl, Br, or    I,-   b) BH₃, B(CH₃)₃, GaH₃, AlH₃, Al(acetate)(OH)₂, Al[OCH(CH₃)₂]₃,    Al(OCH₃)₃, Al(OC₂H₅), Al₂O₃, (CH₃)₃Al, Ti[OCH(CH₃)₂]₃Cl,    Ti[OCH(CH₃)₂]₄, methylaluminum    di-(2,6-di-tert-butyl-4-methylphenoxide), methylaluminum    di-(4-brom-2,6-di-tert-butylphenoxide), LiClO₄,-   c) Mg(acetate)₂, Zn(acetate)₂, Ni(acetate)₂, Ni(NO₃)₂, Co(acetate)₂,    Co(NO₃)₂, Cu(acetate)₂, Cu(NO₃)₂, Li(acetate), Zr(acetylacetonate)₄,    Si(acetate)₄, K(acetate), Na(acetate), Cs(acetate), Rb(acetate),    Mn(acetate)₂, Fe(acetate)₂, Bi(acetate)₃, Sb(acetate)₃,    Sr(acetate)₂, Sn(acetate)₂, Zr(acetate)₂, Ba(acetate)₂,    Hg(acetate)₂, Ag(acetate), Tl(acetate)₃,-   d) Sc(fluoromethansulfonate)₃, Ln(fluoromethanesulfonate)₃,    Ni(fluoromethanesulfonate)₂, Ni(tosylate)₂,    Co(fluoromethanesulfonate)₂, Co(tosylate)₂,    Cu(fluoromethanesulfonate)₂ and Cu(tosylate)₂.

In one or more embodiments, the at least one Lewis acid is ametal-containing compound selected from the group consisting of

-   a) AsF₃, AsCl₃, AsBr₃, AsI₃, GaF₃, GaCl₃, GaBr₃, GaI_(a), BF₃, BCl₃,    BBr₃, BI₃, BF₃.(C₂H₅)₂O, BCl₃.(C₂H₅)₂O, BBr₃.(C₂H₅)₂O, BI₃.(C₂H₅)₂O,    BF₃.S(CH₃)₂, BCl₃.S(CH₃)₂, BBr₃.S(CH₃)₂, BI₃S(CH₃)₂, AlF₃, AlCl₃,    AlBr₃, AlI₃, (C₂H₅)₂AlCl, SbF₃, SbCl₃, SbBr₃, SbI₃, SbF₅, SbCl₅,    SbBr₅, SbI₅, SnF₂, SnCl₂, SnBr₂, SnI₂, MgF₂, MgCl₂, MgBr₂, MgI₂,    MgF₂.O(C₂H₅)₂, MgCl₂.O(C₂H₅)₂, MgBr₂.O(C₂H₅)₂, MgI₂.O(C₂H₅)₂, ZnF₂,    ZnCl₂, ZnBr₂, ZnI₂, BiF₃, BiCl₃, BiBr₃, BiI₃, FeF₂, FeCl₂, FeBr₂,    FeI₂, TiF₂, TiCl₂, TiBr₂, TiI₂, TiF₄, TiCl₄, TiBr₄, TiI₄, NbF₅,    NbCl₅, NbBr₅, NbI₅, NiF₂, NiCl₂, NiBr₂, NiI₂, CoF₂, CoCl₂, CoBr₂,    CoI₂,-   b) Al[OCH(CH₃)₂]₃, Al(OCH₃)₃, Al(OC₂H₅), Al₂O₃, (CH₃)₃Al,    Ti[OCH(CH₃)₂]₃Cl, Ti[OCH(CH₃)₂]₄, methylaluminum    di-(2,6-di-tert-butyl-4-methylphenoxide), methylaluminum    di-(4-brom-2,6-di-tert-butylphenoxide), LiClO₄,-   c) Mg(acetate)₂, Zn(acetate)₂, Ni(acetate)₂, Ni(NO₃)₂, Co(acetate)₂,    Co(NO₃)₂, Cu(acetate)₂, Cu(NO₃)₂,-   d) Sc(fluoromethansulfonate)₃, Ln(fluoromethanesulfonate)₃,    Ni(fluoromethanesulfonate)₂, Ni(tosylate)₂,    Co(fluoromethanesulfonate)₂, Co(tosylate)₂,    Cu(fluoromethanesulfonate)₂ and Cu(tosylate)₂.

In one or more specific embodiments, the at least one Lewis acid is ametal-containing compound selected from the group consisting of AlX₃,SnX₂, MgX₂, MgX₂.O(C₂H₅)₂, ZnX₂, BiX₃, FeX₂, Al[OCH(CH₃)₂]₃, Al(OCH₃)₃,and Al(OC₂H₅)₃, whereby X in each case denotes F, Cl, Br or I.

In other specific embodiments, the at least one Lewis acid is ametal-containing compound selected from the group consisting of AlCl₃,SnCl₂, MgCl₂, MgCl₂.O(C₂H₅)₂, ZnCl₂, BiCl₃, FeCl₂, Al[OCH(CH₃)₂]₃,Al(OCH₃)₃, and Al(OC₂H₅)₃.

In a further embodiment, mixtures of different Lewis acids can be used.

In a specific embodiment, the presently claimed invention relates to aprocess for the preparation of a compound of general formula (I)

wherein R¹ and R³, mutually independently, in each case denote a moietyselected from the group consisting of methyl, ethyl, propyl, isopropyl,n-butyl, isobutyl, tert-butyl, n-pentyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 3-methylbutyl, hexyl, 2-ethylhexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclohexyl, sec-butyl,CH₃—CH₂—C(CH₃)₂—, 1,1,3,3,-tetramethylbutyl, and unsubstituted phenyl;and R² and R⁴, in each case denote H;comprising at least the step of reacting at least one compound ofgeneral formula (II)

wherein R¹ and R³, mutually independently, in each case denote a moietyselected from the group consisting of methyl, ethyl, propyl, isopropyl,n-butyl, isobutyl, tert-butyl, n-pentyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 3-methylbutyl, hexyl, 2-ethylhexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclohexyl,1,1,3,3,-tetramethylbutyl, sec-butyl, CH₃—CH₂—C(CH₃)₂—, andunsubstituted phenyl; and R² and R⁴, in each case denote H;with at least one compound of general formula (III)

wherein R⁵ in each case denotes a moiety selected from the groupconsisting of methyl, ethyl and iso-propyl;in the presence of at least one metal-containing compound selected fromthe group consisting of AlCl₃, SnCl₂, MgCl₂, ZnCl₂, BiCl₃, FeCl₂,Al[OCH(CH₃)₂]₃, Al(OCH₃)₃, and Al(OC₂H₅)₃.

In one or more embodiments, the molar ratio of the at least one compoundof general formula (II) to the at least one compound of general formula(III) is in in the range of 5.0:1.0 and 2.5:1.0, more specifically themolar ratio of the at least one compound of general formula (II) to theat least one compound of general formula (III) is in in the range of3.0:1.0 and 2.6:1.0.

In one or more embodiments, the concentration of the at least onemetal-containing compound in relation to the at least one compound ofgeneral formula (II) is in in the range of 1 mol-% to 60 mol-%, morespecifically in the range of 5 mol-% to 50 mol-%, most specifically inthe range of 30 mol-% to 50 mol-%. The at least one metal-containingcompound is added to the mixture containing at least one compound ofgeneral formula (II) and the at least one compound of general formula(III) in one portion or in several portions such as 2, 3 or 4 portions.

In one or more embodiments, the at least one compound of general formula(II) and the at least one compound of general formula (III) are reactedin at least one inert organic solvent having a boiling point in therange of 80° C. to 185° C. More specifically, the at least one compoundof general formula (II) and the at least one compound of general formula(III) are reacted in at least one inert organic solvent selected fromthe group consisting of toluene, xylene, ortho-xylene, para-xylene,mesitylene, cyclohexane, cyclopentanone, benzonitrile, chlorobenzene,1,2-dichlorobenzene, 1,2-dichloroethane, dibutylether, anisol,butylacetate, methylethylketone, methylisobutylketone, pinacolone,dimethylformamide, and acetonitrile, most specifically the at least onecompound of general formula (II) and the at least one compound ofgeneral formula (III) are reacted in at least one inert organic solventselected from the group consisting of toluene, xylene, mesitylene, andcyclohexane. The aforementioned inert organic solvents can also be usedas mixtures of different solvents.

In an alternative embodiment, the reaction of the at least one compoundof general formula (II) and the at least one compound of general formula(III) does not require the addition of organic solvents. In case thereaction of the at least one compound of general formula (II) and the atleast one compound of general formula (III) is carried out without anyadditional solvent, the at least one compound of general formula (II) isused at a molar concentration in the range of 1.0 M to 8.0 M, morespecifically at a molar concentration in the range of 3.0 M to 8.0 M.

In one or more embodiments, the at least one compound of general formula(II) and the at least one compound of general formula (III) are reactedin an inert solvent, whereby the molar concentration of the at least onecompound of general formula (II) is in the range of 1.0 M to 8.0 M, morespecifically at a molar concentration in the range of 3.0 M to 8.0 M,most specifically at a molar concentration in the range of 5.0 M to 8.0M.

The time for fully converting the at least one compound of generalformula (II) to the at least one compound of general formula (I) dependson the amount of catalyst that is used and the reaction temperature.However, in one or more embodiments, the at least one compound ofgeneral formula (II) and the at least one compound of general formula(III) are reacted at a temperature in the range of 70° C. to 140° C. fora period in the range of 2 to 20 hours, more specifically at atemperature in the range of 85° C. to 105° C. for a period in the rangeof 3 to 20 hours.

The at least one compound of general formula (I) can be isolated andpurified by a variety of different methods. However, in one aspect ofthe presently claimed invention the at least one compound of generalformula (I) is purified and isolated by applying the following steps:

-   (a) adding an inert organic solvent and water;-   (b) separating the organic phase from the water phase;-   (c) optionally washing the organic phase with a 1N aqueous solution    of hydrochloric acid;-   (d) washing the organic phase with water;-   (e) filtering the organic phase and drying of the thus obtained    residue to obtain the at least one compound of general formula (I).

In another aspect, the presently claimed invention is directed to theuse of a compound that is obtained by the inventively claimed processfor enhanced oil recovery.

EXAMPLES Preparation of2-(bis(2-hydroxy-3,5-di-tert-butylphenyl)methyl)-4,6-di-tert-butylphenol(Example 1) [CAS No. 143560-44-5]

2,4-di-tert.-Butylphenol was melted in an oven at 80° C. 41.6 g (200mmol) of melted 2,4-di-tert.-butylphenol was directly weighted into a250 mL-flask. 30 mL toluene (abs.) was added and under stifling themixture was heated up to 50° C. until a clear solution was obtained. Theconcentration of 2,4-di-tert.-butylphenol in toluene was 6.66 M. 12.3 mL(73 mmol) Triethylorthoformiate were added and a clear solution was thenobtained. 8 g (80 mmol) Magnesium chloride (salt A) was added. A whitesuspension was obtained. The reaction mixture was heated up to 100° C.,a nearly green solution was obtained. After 8 hours at 100° C. a brownsuspension formed.

The reaction was cooled down to about 60° C. 50 mL toluene (technicalgrade) were added, the reaction mixture was stirred for 10 min. Thesuspension was cooled down to about 25° C. 50 mL of deionized water wasadded. The temperature rose to 33° C. The reaction mixture was leftunder stirring for 10 min. After stopping the stirrer, 2 phases wererapidly obtained: the solid remained suspended in the organic phase. Theseparation of the phases was done in a 500 mL separatory funnel. A clearwater phase with a pH of about 10 was obtained. The organic phase waswashed successively with: (i) 50 mL water with 0.2 mL 1N HCL solution; apH of 5 was obtained, the extraction was followed by a rapid separation,the aqueous phase was separated and (ii) 50 mL water; a pH of 6 wasobtained, the extraction was followed by a rapid separation, the aqueousphase was separated. The solid was dispersed in the organic phase.

The organic phase containing the suspended solid was filtered over aBuchner funnel. The filter cake was washed twice with little toluene (intotal about 50 mL). The drying of the filter cake was done in the vacuumoven at 80° C. until constant weight. The desired product was obtainedas a white solid (27.7 g, 66% of theory).

The above-identified procedure was carried out with additional salts atdifferent conditions (table 1).

TABLE 1 Concentration of the Concentration salt based Excess of Reactiontime of Phenol on phenol triethylorthoformiate [h] and temperature YieldExample Salt [M] [mol.-%] [mol.-%] Solvent [° C.] [%] 2 AlCl₃ 3.33 5 10Toluene 17/100 14 3 SnCl₂ 3.33 5 10 Toluene 17/100 35 4 MgCl₂ 3.33 5 10Toluene 17/100 45 5 ZnCl₂ 3.33 5 10 Toluene 17/100 48 6 BiCl₃ 3.33 5 10Toluene 17/100 <10 7 FeCl₂ 3.33 5 10 Toluene 17/100 24 8 Al[OCH(CH₃)₂]₃3.33 5 + 5 10 Toluene 17/100 31 9 Al[OCH(CH₃)₂]₃ 3.33 20 10 Toluene17/100 25 10 Al[OCH(CH₃)₂]₃ 3.33 40 10 Toluene 17/100 31 11 MgCl₂ 3.33 110 Toluene 17/100 25 12 MgCl₂ 3.33 2.5 10 Toluene 17/100 27 13 MgCl₂3.33 5 10 Toluene 17/100 45 14 MgCl₂ 6.67 50 10 Butyl  6/100 35 acetate15 MgCl₂ 6.67 50 10 Xylene  6/100 70 16 MgCl₂ 6.67 50 10 Mesitylene 6/100 69 17 MgCl₂ 6.67 50 10 Cyclohexane 20/85  75 18 MgCl₂ 6.67 50 10Chlorobenzene  6/100 64 19 MgCl₂ 6.67 50 10 1,2-  6/100 72Dichlorobenzene 20 MgCl₂ 6.67 50 10 1,2- 20/85  74 Dichloroethane 21MgCl₂ 6.67 50 10 Dibutyl-  6/100 63 ether 22 MgCl₂ 6.67 50 10 Anisol 6/100 67 23 MgCl₂ 6.67 50 10 Butyl  6/100 69 acetate 24 MgCl₂ 6.67 5010 Methyl 20/85  18 ethylketone 25 MgCl₂ 6.67 50 10 DMF 6/100 29 26MgCl₂ 6.67 50 10 Acetonitrile 20/85  62

Preparation of2-[bis[3,5-bis(1,1-dimethylpropyl)-2-hydroxy-phenyl]methyl]-4,6-bis(1,1-dimethylpropyl)phenol(Example 27)

197 g (800 mmol) of 2,4-di-tert-amylphenol was solubilized in 120 mLtoluene in a 1.5 L-flask. 32 g (320 mmol) magnesium chloride was added.50 mL (292 mmol) Triethylorthoformiate was added to the resultingsuspension. The reaction mixture was heated to 100° C., a green solutionwas obtained. After 20 hours at 100° C. a yellow suspension formed.

The reaction mixture was cooled down to about 20° C. 200 mL toluene and200 mL ethyl acetate were added. The organic phase was washed 3 timeswith 200 mL deionized water. The solvent was eliminated by distillation.250 mL ethanol was added to the crude and stirred at 40° C. Theresulting suspension was cooled down to 0° C., filtered over a funnel.The filter cake was washed with cold ethanol and dried in the vacuumoven at 80° C. until constant weight. The desired product was obtainedas a white solid (94 mg, 51% of theory).

Preparation of2-[bis(5-tert-butyl-2-hydroxy-3-sec-butyl-phenyl)methyl]-4-tert-butyl-6-sec-butyl-phenol(Example 28)

173 g 2-secbutyl-4-tert-butylphenol (800 mmol) was solubilized in 120 mLtoluene in a 1.5 L-flask. 32 g (320 mmol) magnesium chloride was added.50 mL (292 mmol) Triethylorthoformiate was added to the resultingsuspension. The reaction mixture was heated to 100° C., a green solutionwas obtained. After 20 hours at 100° C. a yellow suspension formed. Thereaction mixture was cooled down. 300 mL toluene and 300 mL ethylacetate were added. The organic phase was washed 3 times with 200 mLdeionized water. The solvent was eliminated by distillation. 200 mLhexane was added to the crude, the resulting suspension was filteredover a funnel. The filter cake was washed with hexane and dried in thevacuum oven at 80° C. until constant weight. The desired product wasobtained as a white solid. (82 g, 49% of theory). Additional product(15.1 g, 9% of theory) was obtained from the mother liquor afterelimination of the solvent and crystallization in hexane, filtration,washing with hexane and subsequent drying.

Preparation of2-[bis(5-tert-butyl-2-hydroxy-3-isopropyl-phenyl)methyl]-4-tert-butyl-6-isopropyl-phenol(Example 29)

176 g (800 mmol) 4-tert-butyl-2-isopropylphenol was solubilized in 120ml toluene in a 1.5 L-flask. 32 g (320 mmol) magnesium chloride wasadded. 50 mL (292 mmol) Triethylorthoformiate was added to the resultingsuspension. The reaction mixture was heated to 100° C., a green solutionwas obtained. After 20 hours at 100° C. a brown suspension formed.

The reaction mixture was cooled down. 400 mL toluene was added. Theorganic phase was washed 3 times with 200 mL deionized water. Thesolvent was eliminated by distillation. 200 mL hexane were added to thecrude, the resulting suspension was filtered over a funnel. Thefiltercake was washed with hexane and dried in the vacuum oven at 80° C.until constant weight. The desired product was obtained as a whitesolid. (46.6 g, 30% of theory). Additional product (34.4 g, 22% oftheory) was obtained from the mother liquor after elimination of thesolvent and crystallization in hexane, filtration, washing with hexaneand subsequent drying.

Preparation of2-[bis(2-hydroxy-3,5-diphenyl-phenyl)methyl]-4,6-diphenyl-phenol(Example 30)

200 g (800 mmol) 2,4-diphenylphenol was suspended in 120 mL toluene in a1.5 L-flask. 32 g (320 mmol) magnesium chloride was added. 50 mL (292mmol) Triethylorthoformiate was added to the suspension. The reactionmixture was heated to 100° C., after 30 min the thick suspension wasdiluted with additional 200 mL toluene, after 2 hours again 100 mLtoluene was added. After 8 hours at 100° C. a fine yellow suspensionformed.

The reaction mixture was cooled down. 200 mL water was added followed byaddition of 250 mL ethylacetate. The organic phase, a suspension, waswashed 3 times with 200 mL deionized water. The suspension was filteredover a funnel. The filter cake was washed with ethylacetate and dried inthe vacuum oven at 80° C. until constant weight. The desired product wasobtained as a white solid. (72.9 g 37% of theory).

What is claimed is:
 1. A process for the preparation of a compound ofgeneral formula (I)

wherein R¹, R², R³ and R⁴, mutually independently, in each case denoteH; F; Cl; Br; I; —OH; —NO₂; —CN; —C(═O)—R⁶; —C(═O)—O—R⁷; —O—C(═O)—R⁸;—NH—C(═O)—R⁹; —C(═O)—NH₂; —C(═O)—NH—R¹⁰; —C(═O)—NR¹¹R¹²; —O—R¹³; —S—R¹⁴;—S(═O)—R¹⁵; —S(═O)₂—R¹⁶; (unsubstituted or at least monosubstitutedalkyl; unsubstituted or at least monosubstituted heteroalkyl;unsubstituted or at least monosubstituted cycloalkyl; unsubstituted orat least monosubstituted cycloalkenyl; unsubstituted or at leastmonosubstituted heterocycloalkyl; unsubstituted or at leastmonosubstituted heterocycloalkenyl or unsubstituted or mono- orpolysubstituted aryl; and R⁶, R⁷, R⁸, R⁹; R¹⁰; R¹¹; R¹²; R¹³; R¹⁴; R¹⁵and R¹⁶, mutually independently, in each case denote unsubstituted or atleast monosubstituted alkyl; unsubstituted or at least monosubstitutedalkenyl or unsubstituted or at least monosubstituted heteroalkyl; theprocess comprising at least the step of reacting at least one compoundof general formula (II)

wherein R¹, R², R³ and R⁴, mutually independently, in each case denoteH; F; Cl; Br; I; —OH; —NO₂; —CN; —C(═O)—R⁶; —C(═O)—O—R⁷; —O—C(═O)—R⁸;—NH—C(═O)—R⁹; —C(═O)—NH₂; —C(═O)—NH—R¹⁰; —C(═O)—NR¹¹R¹²; —O—R¹³; —S—R¹⁴;S(═O)—R¹⁵; —S(═O)¹⁶; unsubstituted or at least monosubstituted alkyl;unsubstituted or at least monosubstituted heteroalkyl; unsubstituted orat least monosubstituted cycloalkyl; unsubstituted or at leastmonosubstituted cycloalkenyl; unsubstituted or at least monosubstitutedheterocycloalkyl; unsubstituted or at least monosubstitutedheterocycloalkenyl; or unsubstituted or mono- or polysubstituted aryl;and R⁶, R⁷, R⁸, R⁹; R¹⁰; R¹¹; R¹²; R¹³; R¹⁴; R¹⁵ and R¹⁶, mutuallyindependently, in each case denote unsubstituted or at leastmonosubstituted alkyl; unsubstituted or at least monosubstituted alkenylor unsubstituted or at least monosubstituted heteroalkyl; with at leastone compound of general formula (III)

wherein R⁵, mutually independently, in each case denotes unsubstitutedor at least monosubstituted alkyl; in the presence of at least one Lewisacid.
 2. The process of claim 1, wherein the at least one Lewis acid isa metal-containing compound selected from the group consisting of a)AsX₃, GaX₃, BX₃, BX₃.(C₂H₅)₂O, BX₃.S(CH₃)₂, AlX₃, (C₂H₅)₂AlX, SbX₃,SbX₅, SnX₂, MgX₂, MgX₂.O(C₂H₅)₂, ZnX₂, BiX₃, FeX₂, TiX₂, TiX₄, NbX₅,NiX₂, CoX₂, HgX₂, wherein X in each case denotes F, Cl, Br or I, b) BH₃,B(CH₃)₃, GaH₃, AlH₃, Al(acetate)(OH)₂, Al[OCH(CH₃)₂]₃, Al(OCH₃)₃,Al(OC₂H₅), Al₂O₃, (CH₃)₃Al, Ti[OCH(CH₃)₂]₃Cl, Ti[OCH(CH₃)₂]₄,methylaluminum di-(2,6-di-tert-butyl-4-methylphenoxide), methylaluminumdi-(4-brom-2,6-di-tert-butylphenoxide), LiClO₄, c) Mg(acetate)₂,Zn(acetate)₂, Ni(acetate)₂, Ni(NO₃)₂, Co(acetate)₂, Co(NO₃)₂,Cu(acetate)₂, Cu(NO₃)₂, Li(acetate), Zr(acetylacetonate)₄, Si(acetate)₄,K(acetate), Na(acetate), Cs(acetate), Rb(acetate), Mn(acetate)₂,Fe(acetate)₂, Bi(acetate)₃, Sb(acetate)₃, Sr(acetate)₂, Sn(acetate)₂,Zr(acetate)₂, Ba(acetate)₂, Hg(acetate)₂, Ag(acetate), Tl(acetate)₃, d)Sc(fluoromethansulfonate)₃, Ln(fluoromethanesulfonate)₃,Ni(fluoromethanesulfonate)₂, Ni(tosylate)₂, Co(fluoromethanesulfonate)₂,Co(tosylate)₂, Cu(fluoromethanesulfonate)₂, and Cu(tosylate)₂.
 3. Theprocess of claim 1, wherein the at least one Lewis acid is ametal-containing compound selected from the group consisting of AlX₃,SnX₂, MgX₂, ZnX₂, BiX₃, FeX₂, Al[OCH(CH₃)₂]₃, Al(OCH₃)₃ and Al(OC₂H₅)₃,wherein X in each case denotes F, Cl, Br, or I.
 4. The process of claim3, wherein X denotes Cl.
 5. The process of claim 1, wherein the at leastone Lewis acid is a metal-containing compound selected from the groupconsisting of AlCl₃, SnCl₂, MgCl₂, ZnCl₂, BiCl₃, FeCl₂, Al[OCH(CH₃)₂]₃,Al(OCH₃)₃, and Al(OC₂H₅)₃.
 6. The process of claim 1, wherein the molarratio of the at least one compound of general formula (II) to the atleast one compound of general formula (III) is in the range of 5.0:1.0and 2.5:1.0.
 7. The process of claim 1, wherein the concentration of theat least one metal-containing compound in relation to the at least onecompound of general formula (II) is in the range of 1 mol-% to 60 mol-%.8. The process of claim 1, wherein the at least one compound of generalformula (II) and the at least one compound of general formula (III) arereacted in at least one inert organic solvent selected from the groupconsisting of toluene, xylene, ortho-xylene, para-xylene, mesitylene,cyclohexane, cyclopentanone, benzonitrile, chlorobenzene,1,2-dichlorobenzene, 1,2-dichloroethane, dibutylether, anisol,butylacetate, methylethylketone, methylisobutylketone, pinacolone,dimethylformamide, and acetonitrile.
 9. The process of claim 1, whereinthe at least one compound of general formula (II) and the at least onecompound of general formula (III) are reacted at a temperature in therange of 70° C. to 140° C. for a period in the range of 2 to 20 hours.10. The process of claim 1, wherein the at least one compound of generalformula (II) and the at least one compound of general formula (III) arereacted in an inert solvent, wherein the molar concentration of the atleast one compound of general formula (II) is in the range of 1.0 M to8.0 M.
 11. The process of claim 1, wherein R⁵ denotes unsubstituted C₁₋₅alkyl.
 12. The process of claim 1, wherein R¹ and R³, mutuallyindependently, in each case denote H, F, Cl, Br, I, unsubstituted or atleast monosubstituted C₁₋₁₂ alkyl, unsubstituted or at leastmonosubstituted C₃₋₈ cycloalkyl, or unsubstituted or mono- orpolysubstituted aryl; and R² and R⁴, in each case denote H.
 13. Theprocess of claim 1, wherein R¹ and R³, mutually independently, in eachcase denote a moiety selected from the group consisting of methyl,ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl,1,1-dimethylpropyl, 2,2-dimethylpropyl, 3-methylbutyl, hexyl,2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,cyclopentyl, cyclohexyl, 1,1,3,3,-tetramethylbutyl, sec-butyl,CH₃—CH₂—C(CH₃)₂—, and unsubstituted phenyl; and R² and R⁴, in each casedenote H.
 14. The process of claim 1, wherein the compound of generalformula (I) is purified and isolated by applying the following steps:(a) adding an inert organic solvent and water to provide an organicphase and a water phase; (b) separating the organic phase from the waterphase; (c) optionally washing the organic phase with a 1N aqueoussolution of hydrochloric acid; (d) washing the organic phase with water;(e) filtering the organic phase to provide a residue and drying theresidue.